Liquefaction apparatus



July 3, 1-923.

1,676,225 R. c. TOLMAN ET AL LIQUEFACTION APPARATUS Original Filed Sept. 16. 1922 5 Sheets-Sheet 1 July 3, 1928. 1,676,225

R. c. TOLMAN Er AL LIQUEFACTION APPARATUS Original Filed Sept. 16. 1922 3 51 134 ,2

TEMPERATURE fl Jri/YXENVORS wrmass I fra I 9 hM/i -zz A TTORNE V5 July 3, 1928. 1,676,225

R. C. TOLMAN ET AL LIQUEFACTION APPARATUS Original Filed Sept. 16. 1922 3 Sheets-Sheet 3 Patent ed July 3, 1 928.

UNITED) STATES v 1,676,225 PATENT OFFICE.

' RICHARD C. TOLMAN, OF WASHINGTON, DISTRICT OF. COLUMBIA; WILLIAMJ DE BAUFRE, OF LINCOLN, NEBRASKA; JOHN W. DAVIS, OF WASHINGTON, DISTRICT OF COLUMBIA; AND MONTAGUE H. ROBERTS, OF, ENGLEWOOD, NEW. JERSEY, ASSIGNORS TO SAMUEL G. ALLEN, TRUSTEE.

LIQUEFACTION APPARATUS.

Original application filed September 16, 1922, Serial No. 588,530. Divided and this application filed December 28, 1923.

, This invention relates to improvements in the art of separation of various constituents of'air, natural and other gases; audit is especially useful where the substance (or 5 substances) to be separated is volatile and stances as helium, the liquefaction processes employed ,in standard air separation methods have been followed, but such processes, while measurably successful for such purpose, have not proven to be successful in the separation of helium, the cost of separating a useful quality of helium being prohibitive. In the air separation processes, no one of the main products has been comparatively low in boiling point relative to the other chief constituents. In applying these processes to the separation of helium, the nitrogen of the gaseous mixture has been liquefied and separated from the other substances so that the liquid nitrogen could be used for cooling purposes, the liquefied substances being repeatedly drawn away. for this purpose as liquefaction took place. When this is done in the 'separation of helium, which constitutes but a small percentage of the gas and which, as stated, has a very low boilmg point relative Ito the other substances and is not very soluble in their liquids, the ther mo-dynamic efficiency is solow as to make the cost of production prohibitive. (Helium has a boiling point of approximately 4 C. absolute and nitrogen, which is the nearest to it, has'fl a boiling point of approximately 79 C. absolute.)

In the air separation processes, mosteifective separation may be obtained by rectification at low pressure, but where rectification is not desirable, as we have found when helium, for example, is to be separated, it is preferable to use relatively high pressures (in the neighborhood of 30 atmos- Serial No. 683,276.

with such other objects as may hereinafterappear, or are incident to our invention, by means of a method which we have diagrammatically illustrated in the accompanying drawings, wherein: Y

Fig. 1 is a diagrammatic view of apps.- ratus suitable for carrying out ourinvention; Fig. 2 is a curve illustrating the cycle and the principles of our invention; Fig. 3 illustrates a modification of the invention; and Fig. 4 is a section taken on the line 44 of Fig. 1. I s; Before passing to a detailed description of the method and apparatus which we employ, certain of the general princi les upon which the invention proceeds will e briefly summarized as follows:

For a gas of given constituency or composition, if phase equilibrium is maintained between the vapor and the condensate and no liquid is removed, then under constant pressure a given temperature must be reached in order to liquefy the same or to liquefy a given proportion of the substances which it is desired to remove by liquefaction. If as liquefaction proceeds, liquid is abstracted, the composition of the remaining gas or the remaining mixture of liquid and gas is altered and a still lower temperature must be obtained in order to liquefy the remaining gas or to liquefy the substances which are not desired. This latter is what has heretofore been done with the result that the liquefaction curve, instead of being fiat or substantially horizontal, is shar 1y inclined, the progressive removal of the iquid or condensate necessarily involving a regressive lowering of the temperature w ich had to be obtained in order to carryon the liquefaction process. This makes the approximation of the reversible cycle impractical and, therefore, involves the use of much more power than we have found actually necessary. By our process we propose to produce a substantially flat lique- 'fact1on curve as. we do not abstract the straction of a large quantity of heat but by means of a relatively small drop in temperature, providing that the composition of the mixture is not altered during liquefaction. Thisv has apparently not been heretofore realized and is, among other things, what we accomplish by our process.

It has been realized by others before that a truly reversible cycle would be thermodynamically the most efficient but such a cycle, in so far as we are aware, has not heretofore been approximated. We have discovered that to obtain. such a cycle, the incoming fluid should .be liquefied by boill; ing or evaporating a returning fluid of sub stantiall the same composition. If the return fluid be of. diflerent composition, then there is an unnecessary increase in entropy and a consequent increase in power uselessly expended. Heretofore, in this art, it has been assumed that the increase in entropy was largely attributable to heat leaks in the system, but we have found that this is a negligible factor and thatone of'the primary causes of the increase in entropy is that the incoming fluid has been liquefied by evaporating a return flgid of materially different composition. In'accordance with our process, we propose to subject the incoming fluid to a return fluid of substantially the same composition, save with respect to the element which is to be separated out, and we thus obtain as truly a reversible cycle as it is possible to obtain.

The reasons which make it desirable to keep the vapor and liquid of the incoming fluid in contact with one another during liquefaction, apply also to the return fluid evaporated by means of the incoming-fluid.

This return fluid should be evaporated in such manner that the vapor formed is kept in contact with the liquid and equilibrium" maintained as nearly as possible for. the reason that thereby a minimum increase only intemperature is required for evaporation which, of course, involves a minimum.

power consumption. Stated in other words,

a high degree of efficiency are to be obtained,

the pressure drop between the incoming and the returning streams of fluid should be kept low and we prefer the minimum drop required toproduce the difference in temperature necessary to secure the heat transfer through the metal parts and to maintain a flow through the system; whereas heretofore it has been the practice to have a very large drop in pressure in certain parts of the cycle, often as high as 200 to 1 (and never materially below 3.0 to 1) which, of course, involves the useless expenditure of a large amount of power.

We have also found that the purity of product, for any attainable temperature, .is increased if the separation be effected at high ressure, say for example, in the neighborliood of 30 atmospheres which should obtain through the cycle with substantial constancy. Heretofore it has not been; the practice to maintain a high substantially constant pressure but on the contrary in the various steps of cooling, liquefying and rectifying up till purification, the pressure has been widely dropped, involving power losses due to thermo-dynamic inefliciency.

We have also found that the solubility of the substance to be separated, in the liquids of the condensed portions of the gas, has an important bearing on the yield or recovery; and with such substances as helium, although they are relatively not thus soluble, their solubility in the liquids. increases with drop in temperature. In any process, therefore, in which the liquefaction is accomplished with a large drop in temperature in the liquefier, the losses in'yield will be greatly increased. We propose to overcome this difliculty by reason of the factthat We secure liquefaction with the minimum drop in temperature in the liquefier; and in addition we propose to remove the liquid condensed beforepurification so as not only to obtam maximum yield, but also avo1d expenditure of power in uselessly cooling a large body of liquid. I

How we put the foregoing andother principles into effect and obtain the advantages herein set forth, will now be described.

scribed.

In the drawings we have shown an intergas to approximately the dew point. It will be observed that there is a large drop in temperature and a considerable quantity of heat abstracted.

The liquefier D comprises the casing 17, the header 16 previously mentioned," the header 18, and the tubes 19 connecting the I headers 16 and '18. This liquefier is preferably substantially horizontally disposed,

"pose.

changer having two units A and B, each with a slight inclination from the horizonunit comprising a casing 7, a pair of headers tal. The reason for inclining the liquefier 8 and'the tubes 9 extending within the casis to cause the liquid condensing in the tubes ing 7 and connecting the two headers. The 19 to flow as rapidly through such tubes as gas is admitted through the valve-indicated the gas or vapor above the liquid is being as a whole by the referrence letter Cpretconducted through the tubes by the pressure erably at a pressure of approximately 80' drop; and this together with the general atmosphres and at a temperature of approxhorizontal disposition of the liquefier enimately 35 C. and passes via the pipe 1Q ables us to more easily keep the incoming into the casing 7 of the unit A, flowing from vapor and liquid in substantial phase equione end "to the other in a tortuous path librium. 'Thus the gases entering the header about the tubes 9, as indicated by arrows, 16 at approximately the dew point are subthe interior of the casing 7 being provided jected to the action of the returning fluid as with a plurality of baflies 11: for this purthey pass through the pipes 19, and practical- (With reference to the pressure and ly all of the readily liquefiable contents of the temperatures given in this specification, atgas are liquefied, the liquid and gas passing tention is directed to the fact that these are along together, in intimate contact with each illustrative merely and are what we have other andin substantial phase equilibrium,

7 found to be preferable in the separation of the composition of the mixture being approxhelium from the particular gas mentioned, imatelyunitorm through the length of the and that for other mixtures and for the tubes 19, with a minimum variation in the separation of other substances different prescomposition of the vapor above the liquid. sures andtemperatures may be required, as The condensate leaving the ,pipes 19 passes the exigencies of the particular case dedown into the chamber 20 connected with mand). 'In passing through the unit A, the the header 18 through a filter 20, and the gases are somewhat cooled by thawing out uncondensed vapors pass out of the header the frozen water vapor in the unit, and they; 18 approximately at a pressure of 30 atleave the unit A by way of the pipe 12, mospheres and a temperature somewhat crossing over at the valve to the pipe 13 lower than the dew point mentioned, say leading to the bottom of the unit B, where for example, minus 117 0., by way of the the gas is cooled by the returnsubstances pipe 21 to the purifier, indicated as a whole going through the tubes 9. A pipe 12, corby the reference letter E.

responding to the pipe 12, is connected with In this manner we are enabled to produce the casing of the unit B so that the interthe fiat liquefaction curve shown in Fig. 2-

changer units may be reversed. The cooled the same being the horizontal portion of the gases pass out of the upper end of the unit curve. From inspection of this curve'it will B through the pipe 14, which is provided be seen that wev are enabled to abstract the with a v suitable shut-off valve 15 and which large amount of heat necessary to liquefy subleads to the heater 16 of the li uefier, instantially all substances save the helium and dicated as a whole by the refei eiice letter the remainingimpurities in the helium, with' D. The gas enters the header 16 approxia minimum drop in temperature, thereby semately at a pressure of 30 atmospheres and curing the greatest poss'ble degree of eflia temperatuie of approximately minus 100 ciency with aminimum expenditure of power- C. which is praeticallythe dew point. An If liquid had been abstracted as condensation outlet pipe 14 leads from the upper end of took ,place,.this portion of thejcurve would the casing 7 of the unit A and is connected drop' off very sharply because of the lower to the pipe 14 and is controlled by a'shuttemperatures which would have to be atofl valve 15, such valve being closed when tained in orderto accomplish liquefact on. the flow is first through the unit A and It will also be observed that the curve is subthen through the 'unit B, as described, the stautially flat untilcomplete liquefaction is valve 15 being closed and the valve 15" beapproached, when it begins to drop off, which ing open when the flow takes place through means that we are'enabled to accomplish the the unit'B and then through'the unit A. 'liquefacton before there is material loss in The first portion of the curve of Fig. 2 yield by virtue of the solubility of the helium illustrates the drop in temperature and the in the liquid condensed, which, as before amount of heat abstracted in cooling the pointed out, increases with drop in temper- III) ature. By not removing the condensed nitrogen and methane durin liquefaction, we additionally obtain the a vantage of high purity of product at comparatively high tem '6 perature and with high thermo-dynamic efliciency.

The gas entering the purifier E is an impure helium, the impurities being a small quantity of nitrogen and methane and traces of other constituents. The gas is subjected to the cooling act-ion of an external cycle of refrigeration and the impurities referred to above are liquefied, collecting in the bottom of the. horizontal casing 22 of the purifier, practically pure helium being drawn off by pipe 23 at a pressure of approximately 30 atmospheres and a temperature of approximately minus 170 C. The liquid condensed in'the purifier is returned tothe liquefier by means'of the pipe 24 provided with a throttling valve 25 which throttles the pressure down tog'preferably 20 atmospheres.

- The liquid condensed in the tubes of the liquefier D is returned to the shell of'the 25 liquefier/ through. the pipe 26 at a pressure of approximately 20 atmospheres obtained by means of a throttling valve 26 and at a temperature of approximately minus 121 C.

The external cycle of refrigeration re- 30 ferred to will be hereinafter described.

The lower portion of the casing 17 of the liquefier is divided into compartments by meansof division walls 27, forming thecompartments (1,7), 0, etc., in .the lower portion of the li uefier casing. The space above the liqui in the casing is also divided into compartments 0;, b, 0', etc., by hanging bafiles or deflection plates 27 From the 'bottom' of each .lower compartment 40 a pipe 28,. 28', etc., leads to the upper region of the next lower compartment. The .return liquid is delivered bypipe 24 to the compartment-a alrdby the pipe 26 to the com-' partment b. Fromcompartment a the liquid not evaporated flows through pipe 28 to compartment b; and from such compartment, the unevaporated liquid flows into compartment 0 by means of.pipe 28'; and so on from compartment to; compartment. Since the pressure of the vapor above compartment-a is the same as the vapor pressure above the mouth of pipe 28, liquid accumulates in compartment on until there is'suflicient head to cause liquid to flow out of pipe 28 into com- 5 partment b, the liquid being discharged into the vapor in the upper compartment a.;- This is true of the other compartments. The arangement of bafiling is, therefore, one tending to keep the liquid and vapor in intimate contact or relation and to maintain phase equilibrium; this purpose being furthered by providing a broad lip or plate 28' at the ori fice ofrthe pipes 28, 28*, etc, over which the discharging liquid flows in a thin, wide proximated, with vapor and liquid in intiis first. through unit B and then through Thus a minumum rise in temperature is,

required to efiect the evaporation necessarfi to secure the required heat transfer, whic means that maximum efliciency is obtained with minimum power expenditure.

Furthermore, the arrangement is one tending to secure the most effective application of the return fluids't-o the down-coming fluids for the reason that-the liquids containing the more readily volatilizable substances are applied to those portions of the tubes carrying the relatively harder vapors to liquefy, that s to say, a true counterfldvv is closely apmate contact and in substantial phase equilibrium, I

The gases returning from the casing 17 to the outlet pipe 29' are delivered to the headers Sand pass through the tubes 9 of the interchanger securing the necessary heat transfer in the interchanger, the gas leaving the casing 17 at approximately a pressure of 20 atmospheres and a temperature of minus 111 (3. and leaving the interchanger at substantiallf 20 atmospheres pressure and a temperature of plus 17 C. It will, of course, be understood that-when the flow of the incoming gas is first through the unit A of the interchanger, the gas from the liquefier is conducted through the tubes of the unit B, cooling the. gases coming into such unit from the unit A, as before described; and when the flow of incoming gas unit A, the gases from the liquefier are led through unit A to cool the gases coming thereinto from unit B. To this endthe outlet pipes leading from the bottom headers of the unit are provided with'valves.

Depending upon how closely equilibrium is attained, the last compartment of the 3 liquefier as we have arranged it, may contain a liquid (such for example, as ethane) which has a relatively high boiling point, that is to say, is of low volatility; and if provision were not made for the abstraction of such liquid from thiscon'1partment, the liquefier would eventually fill with high boiling point liquid and its operation would be greatly impaired, if not destroyed. To meet this condition we take a lead 30 from the bottom of the last compartment and connect it to the return pipe 29 so that any relatively high boiling point liquid which may be present in the liquefier shall be returned along with the gases leaving the upper regions of the liquefier casing to the interchanger interchanger where, of course, such liquid.

will be evaporated and effective heat trans fer secured in the interchanger.

If itwere possible to obtain an absolutely true reversible cycle, the return curve, or rather the curve of the returning fluid under the down-coming fluid, would coincide with theliquefaction curve; but since it is impossible to obtain an absolutely reversible cycle, on account of the necessity for a temperature difference in obtaining the heat transfer and other items incident to operation, in a cycle as truly reversible as it is possible to obtain, the curve of the returning fluid in the liquefier and also in the interchanger should approximately parallel the curve of the incoming fluid in the and liquefier. The return curve produced by our process approximately parallels the down-coming curve with the minimum drop in. teu'iperature between the two streams necessary to secure the requisite heat transfer. This will be seen on inspection of Fig. 2, the stepped portion of the return curve showing the curve of the liquid evaporated and heated on the liquefier. The steps of this portion of the curve are produced by the various compartments of the liquefier, the steps being closer together, i. e. smaller; adjacent those portions of the down-coming curve which are rounded, because at such portions conditions change more rapidly. Thus, in the tubes at the right-hand end of the liquefier, the remain-v ing vapors are rapidly becoming more difficult to liquefy, and, therefore, theoretically, the right-hand end .of the liquefier casing should be split up into a number of small compartments so as to apply correspondingly more easily volatilizable substances in true counter-flow. To this cnd we have progressively diminished the size of the compartments at the right-hand end of the liquefier. Similarly, just below the dew point, for a short interval, the gas becomes rapidly more easily liquefiablc, to meet which condition the compartments at the left-hand end of the liquefier D are also made smaller; The essentially flat portion of the liquefaction curve shows that for an interval there is a greater degree of. constancy in conditions, and durmg this interval, the compartment or compartments of the liquefier/casing may be of larger dimension. The return" curve illustrating the evaporation of the return fluids thus has substantially the same flat characteristic as the liquefaction curve; It will, of course, be understood that the number and size of the compartments-will vary with the particular mixture of gas and the substance separated. Referring now to the cycle of refrigeration by means of which the helium is purified in the purifier E by the liquefaction of the impurities, thisis, as stated, an external cycle, whereas the refrigeration in.

the process up tothis point is accomplished primarily by means of an internal cycle. Any suitable form of refrigeration may be employed for the purifier, but we prefer apparatus such as diagrammatically indicated, preferably using an inert gas which does not condense easily. We mention nitrogen or helium as a suitable medium for I cooled to a temperature of approximately i minus 180 0., the expanded gases being.

led to the purifier at the header 35, passing therefrom through the tubes 36 to the header 37 and from thence to the header I 38 of the interchanger by means of the pipe 39. The gases enter the header 3 8- at a temperature of approximately minus 123 C. and serve to cool the incoming gas. The] gases leave the outlet header 40 of the interchanger at approximately plus 30 C, and are returned to the inlet side of the compressor. The cycle iS' thus, in effect, a substantially closed-one and any make up necessary is supplied to the low pressure side of the compressor at the point marked 41. I

By our apparatus, the purification of the helium can be obtained without dropping,

the pressure and with the abstraction of very little heat notwithstanding the very large drop in temperature required and thus with a minimum of power consumption.

By removing the liquid from the vapor at the end of the liquefier, no power is use lessly expended in cooling a large body of liquid and thus the size and power consumption of the external cycle are reduced to a -minimum. The use of a gas which is not condensed at the lowest temperature obtained gives economy 1n power in the ex ternal cycle and an inert gas maintains safety;

If desired, the helium discharging from the purifier at the pipe 23 may be passed through the purifier casing, and thereafter through the interchanger 33, thus permitting of its use for cooling purposes. an arrangement we have illustrated in Fig.-

v4 of the drawings.

The reason for placing the helium purifier in combination with the auxiliary refrigerating system -in a substantially horizontal position is the desire to keep the liquid and gas in contact "as far as possible in order Such 1 to approximate equilibrium between all of the gas and the liquid, rather than between the gas and the last portion to be condensed out, thus obtaining a higher purity of helium.

The last portion of the curve of Fig. 2 shows the purification by external refrigeration, illustrating the temperature drop and the heat abstracted. It will be seen that the purification is accomplished with the abstraction of relatively'little heat and by a large temperature drop.

The progressive evaporation of the returning liquid provides for the elimina-' tion of high boiling point substances such" as ethane and the higher hydro-carbons, as

,it ensures their collection in the warm end of the liquefier where they can ,be returned to the interchanger Without disorgan-izing or impairing the functioning of the system, particularly the liquefaction step thereof.

. This also obtains maximu'm'efiiciency in the losses in obtaining actualheat transfer, heat leaks and the like, and in which the additional power expended is reduced to a minimum because it is applied at a point where it ismost efiective and where it will not interfere with nor disorganize the other steps of the process. Heretofore, it has been the customary practice to expend power for external refrigeration at other points in the system, particularly during the liquefying where, as pointed out, only a minimum tem- I perature drop is required. In contradistinction we apply our external refrigeration at the point where a maximum drop in temperature with a minimum abstraction of heat is required and where heat leakage into the system is most deleterious. t

amaze The system, therefore, considered 'in its] entirety, is one which lends itselfto increase in general and thermo-dynamic *eflicienc with the production of a high purity pro uctrof extremely high yield, with1 ;a mini-,5 mum power consumption. I

This application is a division {of application filedSept. 16, 1922, Serial No. 588,- 53

We claim:

1. A liquefying apparatus comprising-in combination, interchangers for coolingv the gaseous mixture, a substantially horizontally disposed liquefier for the liquefaction of the major port-ion of the-undesired constituents I of the gas, appropriate connections between the interchangers and 'the liquefier, a chamber communicating with the liquefier and 7 receiving the vapor and condensatel dis-' charged from the liquefier for-separation, means whereby the condensate is utilized: in counter-flow in the liquefier and interchangers, a purifier to whichthe uncondens'ed 7 vapor is led from said chamber, a connection for so leading said vapor, and anQexternal cycle of refrigeratlon for the punfier. I

2. liquefying apparatus comprisingin combination, interchangers for cooling the 1 as, a substantially horizontally disposed iquefier for the liquefaction of the major,

portion of the undesired constitutents of the gas, appropriate connections between theimterchangers and the liquefier, a chamber communicating with said liquefier, said chamber receiving the vapor and condensate discharge from the liquefier for separation, a

purifier to which the uncondensed vapor in 9 said chamber is led, a connection from; the

chamber to the purifier for so leading such vapor, an external cycle of refrigeration for the purifier, and means for utilizing substantially all the liquid condensed in the liquefier and purifier in counter-flow in the liquefier and interc angers. y "i?- In testimony whereof, we havehe'reunto signed pu'r names.

a RICHARD (J. TOLMANL WILLIAM L. DE BAUFR'E. 4

JOHN We DAVIS; MONTAGUE H. ROBERTS. 

